An apparatus and method of producing methanol is provided that reacts a methane-containing gas and an oxygen-containing gas in a reactor to provide a product stream comprising methanol and formaldehyde. The product stream is scrubbed using a process component absorbent. After scrubbing the product stream, unprocessed methane gas is mixed with the methane-containing gas for reprocessing through the reactor while methanol and formaldehyde is sent to a rectification process for removal.

Patent
   9180426
Priority
Jul 29 2004
Filed
Jun 02 2006
Issued
Nov 10 2015
Expiry
Apr 30 2027
Extension
1005 days
Assg.orig
Entity
Small
2
134
currently ok
1. A method for recycling unreacted methane gas from a reaction product gas stream of a homogenous direct partial oxidation methane reactor, the method comprising:
mixing a non-oxidizing coolant with a mixture of methane-containing gas and oxygen-containing gas to inhibit decomposition of formaldehyde while forming the reaction product gas stream, the non-oxidizing coolant including an unheated hydrocarbon or methane-containing gas stream;
feeding the reaction product gas stream into a scrubber;
passing a pre-cooled absorbent through the scrubber;
cooling the reaction product gas stream via direct contact with the pre-cooled absorbent through the scrubber;
removing unreacted methane gas from the reaction product gas stream using the pre- cooled absorbent;
recycling the unreacted methane gas for use in the homogenous direct partial oxidation methane reactor; and
recycling the pre-cooled absorbent for reuse in the scrubber, wherein the pre-cooled absorbent comprises process components of the reaction product gas stream, the scrubber having a lower portion and an upper portion, the temperature of the lower portion being higher than the temperature of the upper portion, the scrubber being further configured such that all liquids flow downward.
8. A method for producing methanol using a homogenous direct partial oxidation reactor, the method comprising:
feeding the reactor with a methane-containing gas and an oxygen-containing gas;
carrying out partial oxidation reaction of methane to form a product gas comprising a mixture of methanol and formaldehyde;
mixing a non-oxidizing coolant with the methane-containing gas and oxygen-containing gas to inhibit decomposition of formaldehyde, the non-oxidizing coolant including a hydrocarbon or methane-containing gas stream;
directing a pre-cooled absorbent to a scrubber;
directing the product gas to said scrubber;
cooling the product gases via direct contact with pre-cooled absorbent within the scrubber;
scrubbing the product gas with said pre-cooled absorbent comprising process components of the product gas in a scrubber, the scrubber having a lower portion and an upper portion, the temperature of the lower portion being higher than the temperature of the upper portion, the scrubber being further configured such that all liquids flow downward;
removing methanol, water, carbon dioxide, and formaldehyde from the product gas to form a spent solvent;
recycling unreacted methane-containing gas from the product gas into the homogenous direct partial oxidation methane reactor; and
recycling spent solvent for reintroduction into the scrubber as the pre-cooled absorbent.
2. A method according to claim 1, wherein the scrubber operates at a pressure of at least about 4MPa and at a temperature of less than about 0° C.
3. A method according to claim 1, wherein the reaction product gas stream comprises a mixture of methanol, formaldehyde, and carbon dioxide, and the pre-cooled absorbent comprises a mixture of methanol and water.
4. A method according to claim 3, further comprising maintaining a steady state balance of methanol between the scrubber and the homogenous direct partial oxidation methane reactor by adding recycled methanol to the scrubber.
5. A method according to claim 3, further comprising condensing methanol and water from the reaction product gas stream and separating a fraction of methanol and water as an absorbant.
6. A method according to claim 3, further comprising substantially removing all of the methanol and formaldehyde entering the scrubber at steady state via a side removal stream.
7. A method according to claim 3, further comprising cooling the spent absorbent prior to its reintroduction in the scrubber.
9. A method according to claim 8, wherein the pre-cooled absorbent comprises methanol and water.
10. A method according to claim 9, wherein recycling the spent solvent comprises substantially removing all of the methanol, water, carbon dioxide, and formaldehyde entering the scrubber at steady state via a side removal stream.
11. A method according to claim 9, wherein recycling the spent solvent comprises cooling the solvent prior to its reintroduction in the scrubber as an absorbent.
12. A method according to claim 9, further comprising cooling the product gas prior to directing the product gas to the scrubber.
13. A method according to claim 9, wherein the product gas is scrubbed at a pressure of at least about 4 MPa and at a temperature of less than about 0° C.

This application is a continuation-in-part application of U.S. application Ser. No. 11/319,093 filed on Dec. 27, 2005, now U.S. Pat. No. 8,202,916 issued Jun. 19, 2012, and is a continuation-in-part application of U.S. application Ser. No. 10/901,717 filed on Jul. 29, 2004, now U.S. Pat. No. 7,179,843 issued Feb. 20, 2007. The disclosures of the above applications are incorporated by reference.

The present disclosure relates to a system and method for producing methanol.

The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.

Methods and apparatuses for the conversion of methane into methanol are known. It is known to carry out a vapor-phase conversion of methane into a synthesis gas (mixture of CO and H2) with its subsequent catalytic conversion into methanol as disclosed, for example, in Karavaev M. M., Leonov B. E., et al “Technology of Synthetic Methanol”, Moscow, “Chemistry” 1984, pages 72-125. However, in order to realize this process it is necessary to provide a complicated equipment, to satisfy high requirements to purity of gas, to spend high quantities of energy for obtaining the synthesis gas and for its purification, and to have a significant number of intermittent stages from the process. Also, for medium and small enterprises with the capacity less than 2,000 tons/day it is not efficient.

Russian Patent No. 2,162,460 includes a source of hydrocarbon-containing gas, a compressor and a heater for compression and heating of gas, a source of oxygen-containing gas with a compressor. It further includes successively arranged reactors with alternating mixing and reaction zones and means to supply the hydrocarbon-containing gas into a first mixing zone of the reactor and the oxygen-containing zone into each mixing zone, a recuperative heat exchanger for cooling of the reaction, mixture through a wall by a stream of cold hydrocarbon-containing gas of the heated hydrocarbon-containing gas into a heater, a cooler-condenser, a partial condenser for separation of waste gasses and liquid products with a subsequent separation of methanol, a pipeline for supply of the waste gas into the initial hydrocarbon-containing gas, and a pipeline for supply of waste oxygen-containing products into the first mixing zone of the reactor.

In this apparatus, however, it is not possible to provide a fast withdrawal of heat of the highly exothermic reaction of oxidation of the hydrocarbon-containing gas because of the inherent limitations of the heat exchanger. This leads to the necessity to reduce the quantity of supplied hydrocarbon-containing gas and, further, it reduces the degree of conversion of the hydrocarbon-containing gas. Moreover, even with the use of oxygen as an oxidizer, it is not possible to provide an efficient recirculation of the hydrocarbon-containing gas due to fast increase of concentration of carbon oxides in it. A significant part of the supplied oxygen is wasted for oxidation of CO into CO2, which additionally reduces the degree of conversion of the initial hydrocarbon-containing gas and provides a further overheating of the reaction mixture. The apparatus also requires burning of an additional quantity of the initial hydrocarbon-containing gas in order to provide a stage of rectification of liquid products with vapor. Since it is necessary to cool the gas-liquid mixture after each reactor for separation of liquid products and subsequent heating before a next reactor, the apparatus is substantially complicated, the number of units is increased, and additional energy is wasted.

A further method and apparatus for producing methanol is disclosed in the patent document RU 2,200,731, in which compressed heated hydrocarbon-containing gas and compressed oxygen-containing gas are introduced into mixing zones of successively arranged reactors, and the reaction is performed with a controlled heat pick-up by cooling of the reaction mixture with water condensate so that steam is obtained, and a degree of cooling of the reaction mixture is regulated by parameters of escaping steam, which is used in liquid product rectification stage.

Other patent documents such as U.S. Pat. Nos. 2,196,188; 2,722,553; 4,152,407; 4,243,613; 4,530,826; 5,177,279; 5.959,168 and International Publication WO 96/06901 disclose further solutions for transformation of hydrocarbons.

It is believed that the existing methods and apparatus for producing methanol can be further improved.

It is accordingly an object of the present disclosure to provide a system and method for producing methanol, which is a further improvement of the existing methods and apparatuses.

It is another feature of the present teachings to provide a system and method for producing methanol which can be used with minimal processing of gas and gas-condensate deposits, and also at any gas consumer, such as power plants, gas distributing and gas reducing stations, chemical production facilities, etc., or small methane producers, (i.e., coal mines, oil production (flares), landfills, farms.)

In keeping with these objects and with others which will become apparent hereinafter, one feature of the present disclosure resides, briefly stated, in a method of producing methanol, which includes the steps of supplying into a reactor a methane-containing gas stream and an oxygen containing gas; oxidizing the methane-containing gas in the reactor using oxygen of the oxygen-containing gas; and, after scrubbing impurities and products of the reaction, including but not limited to carbon dioxide, water, formaldehyde, and methanol, recycling unreacted methane gas into the methane-containing gas stream for further reaction.

Another feature of the present teachings is a system for producing methanol, which has a reactor for receiving and reacting a methane-containing gas stream with an oxygen-containing gas. The system also has a mechanism for supplying into the reactor a non-oxidizing coolant to be directly mixed with a mixture of the methane-containing gas and oxygen containing gas at a later stage of the reaction to inhibit the decomposition of formaldehyde. The coolant functions to inhibit the oxidation or decomposition of the formaldehyde product. Unreacted methane gas is then processed in a scrubber to remove reaction products and contaminants before being recycled back into the methane-containing gas stream. In various embodiments, the scrubber uses a process component absorbent, for example a mixture of methanol and water, and additionally serves as a condenser. The spent absorbent is regenerated after each pass through the scrubber. A side stream may be provided for removal of carbon dioxide, water, formaldehyde, and methanol in an amount substantially equal to that entering the scrubber at steady state.

As can be seen, in accordance with the present teachings, a gas phase oxidation of the methane-containing gas is performed at elevated temperature and pressure in the reaction zone. The reaction mixture is cooled and directed to a scrubber for removal of carbon dioxide, water, methanol, and formaldehyde, and is recycled and combined with the raw methane-containing gas stream. In certain embodiments, cold methane-containing gas is supplied into a regulation zone of the reactor to reduce the reaction temperature, for example by about 30 to about 90° C., and thereby to provide a production and a redistribution of the ratio of products to produce corresponding quantities of methanol and formaldehyde.

The novel features which are considered as characteristic for the present disclosure are set forth in particular in the appended claims. The disclosure itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

FIG. 1 schematically illustrates a system for producing methanol in accordance with the present teachings;

FIG. 2 illustrates a more detailed view of the reactor as shown in the system of FIG. 1; and

FIG. 3 illustrates a more detailed view of the scrubber as shown in the system of FIG. 1.

The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. It should be understood that throughout the drawings, corresponding reference numerals indicate like or corresponding parts and features.

The present disclosure relates to a system and method for reforming hydrocarbon-containing gases, such as alkanes. Alkanes (typically methane and ethane) can be reformed via a homogenous, partial oxidation reaction with oxygen to form oxygenates, for example, methanol and formaldehyde. The partial oxidation reaction of a methane-containing gas may be used to produce primarily methanol, primarily formaldehyde, or virtually any combination of the two products. In order to obtain a desirably high selectivity of oxygenates and avoid deeper oxidation states of the incoming alkanes, the reaction is typically kept very lean of oxygen, for example, between about 1 to about 3%, resulting in a low per-pass conversion. Even then, co-production of deeper oxidized side products such as water and carbon dioxide remain substantial.

The present disclosure includes a method for recovering oxygenates while simultaneously condensing water and methanol from the product gas of a reformation process. An absorption column, also referred to herein as a scrubber, utilizes process components (e.g., methanol and water) as an absorbent to remove formaldehyde and carbon dioxide. The reactor product stream enters the scrubber in the gas phase and a portion of the stream is condensed by and then entrained into the cool absorbent entering the column. As is known in the art, the temperature, pressure, and solvent throughput can be adjusted to enhance recovery as needed to purify the alkane raw material after which it can be sent onto further processing. For most cases, the temperature will be about 0° C. or lower, enhancing the absorption process. This is especially important due to the desirability of recycling the unreacted alkanes and thus boosting overall yield of the otherwise low conversion technology. In various embodiments, the pressure will typically be between 4 and 10 MPa.

As shown in the process flow diagram of FIG. 1, the system includes a reactor 100 which facilitates a gas phase direct partial oxidation of a methane-containing gas. FIG. 2 details the inputs and outputs of the reactor 100 as shown in the system of FIG. 1. The process begins with the reactor 100 where about, for example, 5% conversion of incoming alkanes is achieved having about 40% selectivity to methanol and about 25% selectivity to formaldehyde. The remaining balance of the reaction product is predominately carbon dioxide, following a gas-water shift reaction. The reactor 100 may have an initial reaction zone 102 that can be provided with a device 104 for introducing a heated methane-containing gas stream and a device 105 for introducing an oxygen-containing gas. As explained in more detail below, the oxygen-containing gas preferably has greater than 80% oxygen content to reduce the accumulation of inert gases due to the recycling process.

The reactor 100 may further be equipped with a regulation zone 108 provided with an optional device 110 for introducing a cold hydrocarbon-containing gas stream for reducing the temperature of reaction during operation of the apparatus. In addition, the reactor 100 may be provided with thermal pockets 112 for control and regulation of temperatures in corresponding zones, provided for example with thermocouples. Exiting the reactor 100 is a reaction product gas stream 1 which is at a temperature of about 525° C. and a pressure of about 8 MPa.

With reference to FIG. 1, stream 1 typically enters a “hot in” side of a first heat exchanger 114 that acts as a pre-cooler before the reaction product gas stream enters the absorption phase of the system. The heat exchanger 114 may be sized in order to maximize the heat integration taking place. Stream 2 exits a “hot out” side of the exchanger at a temperature of about 325° C. and is directed to a scrubber 116 for product and side-product recovery. In certain embodiments, stream 2 may be directed to a second heat exchanger, or pre-cooler (not shown), to further reduce the cooling load on the scrubber loop.

The scrubber 116 serves as the liaison between the reaction and recycling gas-phase raw material process, the liquid-phase separation, and the product rectification portion of the overall system. The scrubber 116 prevents the accumulation of CO2 in the hydrocarbon recycle loop while concurrently facilitating the physical capture of formaldehyde. The scrubber 116 of the present disclosure further provides for the condensation of methanol and water that is produced in the reactor and present in the reactor product gas stream, reducing the number of separations within the hydrocarbon recycle loop to a single separation.

FIG. 3 details the inputs and outputs of the scrubber 116 as shown in the system of FIG. 1. The scrubber 116 may utilize a solvent/absorbent that comprises a mixture of reaction product components, namely methanol and water, to physically absorb formaldehyde and C02 from the hydrocarbon gas recycle loop. The efficiency of the scrubber 116 is enhanced by a combination of high operating pressure (4-8 MPa) and low temperatures, for example 25° C. or lower as needed to achieve the desired degree of absorption. As mentioned, the scrubber 116 additionally serves a duel role as a condenser. Both methanol and water will be substantially entrained into the recycling/regenerating absorbent stream. It is envisioned that this design reduces capital costs (due to simplification of the process), operational costs (due to more efficient cooling via direct contact), and the physical size of the process (due to less equipment).

In various embodiments, the lower portion 116a of the scrubber 116 operates at a higher temperature relative to the top portion 116b. It is envisioned that any water content will be removed prior to reaching areas of the column that are cold enough to allow the formation of ice. Since the scrubber 116 does not operate near the triple point of water, the incoming gaseous water will condense and not freeze. As is known, all liquids within the scrubber travel downward. In certain embodiments, it may be beneficial to provide a cooling jacket around the bottom portion of the scrubber.

The regeneration of the absorbent may be accomplished in a variety of ways. In one embodiment, a portion of the pregnant liquid stream 15 may be directed to a cooler 118 via stream 24 to serve as the regenerated, or fresh absorbent in stream 27. In various embodiments, a side-stream may be pulled off of this loop via stream 16 so as to prevent saturating the recycling stream with carbon dioxide and formaldehyde which will be loosely associated with the methanol-water mixture via physical absorbtion. In terms of a mass balance, the side-stream may include substantially all of the water, carbon dioxide, formaldehyde, and methanol entering the scrubber at steady state. Due in part to the known fact that some methanol is expected to escape the scrubber 116 via stream 3 and be recycled to the reactor 100, it may be beneficial to provide a methanol makeup stream, such as stream 22 that combines with the recycling pregnant absorbent stream 24 to form stream 23.

The clean, gaseous hydrocarbons of stream 3 can continue to a hydrocarbon recycle loop for further processing. In one embodiment, the next step may include a purge; for example, stream 18 that may be used to control any nitrogen accumulation within the recycle loop. Stream 4 may then continue to be combined with fresh, raw methane-containing gas, stream 5, to form a mixture via stream 6 that enters a recycle loop compressor 120 to recover any pressure losses from the processing units. In certain embodiments, an additional compressor 122 may be provided to compress the raw methane-containing gas prior to forming stream 6. Exiting the compressor is stream 7 that enters a heat exchanger 114 via a “cool in”. The heated gas, which may reach a temperature of about 275° C., exits the as a “cool out” via stream 8 and may be directed to pre-heaters as discussed below.

The reactor 100 is preferably in communication with a compressor 124 and heater 126 for the supply of compressed and heated oxygen-containing gas at about 8 MPa and about 475° C. via streams 13 and 14, respectively. As mentioned, the raw methane-containing gas is mixed with recycled methane gas from the scrubber 116 and stream 9 may be heated using a pre-heater 128 to heat the gas to about 475° C. prior to entry in the reactor via stream 10. In the event the raw hydrocarbons have a high CO2 content, a portion of the raw hydrocarbons in stream 7 can be mixed with the cooled reaction product gas stream, stream 2, at some point prior to the entry into the scrubber 116 for removal of contaminant gases prior to entering the reactor 100.

In operation, the raw methane-containing gas stream, having a methane content of up to about 98%, and the reduced methane product stream are supplied from their respective source to the pre-heater 128, where the gas is heated to temperature between about 430 to about 470° C. The heated methane-containing gas is then supplied into zone 102 of the reactor 100. Compressed air having a pressure of about 7-8 MPa and with a ratio of about 80% to 100% and, preferably, from about 90% to about 95% oxygen is supplied by the compressor 124 into zone 102 of the reactor 100. In order to limit the amount of N2 within the system, for example to less than about 30%-40%, or to reduce the requisite size of the purge stream to achieve the same, the O2 stream is preferably substantially pure, thus limiting the amount of N2 entering the system.

In various embodiments, an optional second stream of cold methane-containing gas 11, or in other words a coolant at a lower temperature than the gases in the reactor, is supplied through the introducing device 108 into the regulation zone of the reactor 100. This stream is typically regulated by a regulating device 130 that can take the form of any suitable gas supply regulating device, regulating valve, or the like. In various other embodiments, this cold stream, or coolant can comprise a raw hydrocarbon stream, a recycled stream, or a portion or combination of the two. The regulator 130 may be configured to adjust a volume or pressure of a coolant based on system parameters including, but not limited to, pressure, temperature, or reaction product percentages downstream in the system.

The coolant is typically supplied from a coolant source, and if used, functions to reduce the temperature of the partially oxidized methane so as to reduce or limit the continued oxidation or decomposition of formaldehyde. This coolant can comprise any material that is easily separated from the reaction product stream. For example, as better described below, the coolant can include an unheated hydrocarbon or methane-containing gas stream. Additionally, the coolant can comprise any non-oxidizing material that can be easily separated from the reaction. In this regard, the coolant can be gaseous or an aerosol liquid including, for example, carbon dioxide, formaldehyde, methanol, ethanol, water, misted water, steam, and mixtures thereof. It is additionally envisioned that the coolant can be a mixture of recycled reaction products, water, steam, and/or hydrocarbon gases.

Depending on the intended mode of operation of the system, in particular the intended production of methanol or methanol and formaldehyde, the reaction mixture is subjected to the reaction in the reactor 100 without the introduction of the cold hydrocarbon-containing gas if it is desired to produce exclusively methanol. The introduction of the cold hydrocarbon containing gas is used when it is desired to produce methanol and formaldehyde. By introduction of the cold hydrocarbon-containing gas, the temperature of the reaction is reduced for example by 30-90° C. so as to preserve the content of formaldehyde into the separated mixture by inhibiting the decomposition of the formaldehyde to CO2.

A formaldehyde rectification column 132 may be used to separate carbon dioxide and formaldehyde from methanol and water. In various embodiments, the formaldehyde rectification process may involve a flash drum (not shown), a column, or a combination depending on the desired product specifications. In certain embodiments, methane may be absorbed by the absorbent mixture; therefore, a flash drum 140 may be added to the regenerating absorbent loop, fed by stream 28, where the pressure of the stream 25 is dropped to accommodate the disassociation of any dissolved methane. This method will allow the absorbed methane gas to be returned to the hydrocarbon recycle loop. In other embodiments, any absorbed methane may be allowed to remain in solution where it will later be recovered with the exiting CO2 stream and likely incinerated for heating value and/or elimination of any potential VOC's. A single column with a small reflux ratio may be sufficient to disassociate formaldehyde from the absorbent methanol-water mixture. As illustrated in FIG. 1, the pregnant methanol stream, stream 16, enters the rectification column 132 and is separated into a formaldehyde distillate, stream 17, and a bottoms stream, stream 18. It may be desirable to have a certain amount of methanol in the distillate stream since methanol is used as a stabilizer for the production of commercial grade formalin (6-15% alcohol stabilizer, 37% formaldehyde, and the balance being water), as discussed below. By allowing a portion of the heavy key into the distillate stream the separation is more easily achieved; furthermore, process losses typically experienced during absorbent regeneration may subsequently be nullified as methanol within the distillate is used in formalin makeup. Carbon dioxide may also escape at this point and travel with the formaldehyde stream to a formalin blender 136 via stream 17. In various other embodiments, a substantially pure stream of carbon dioxide may be removed for further processing. The remaining methanol-water mixture is directed to a methanol rectification section of the system via stream 18.

Methanol rectification may include one or two columns 134, depending on the desired specifications for the final methanol product. Methanol exits the rectification column via stream 19, of which a portion may be used for the methanol makeup stream of the scrubber loop, stream 22. The remaining methanol may be sent to storage. In embodiments where two columns are used, the methanol makeup, stream 22, would typically be taken from the distillate of the first column. As before, it is desirable for a portion of the heavy key to enter the distillate stream, as will be dictated by the commercial specification for formalin. For methanol rectification, 99% or higher purity is typical and 99.999% is achievable with multiple columns. The bottoms, stream 20, exit the column in liquid phase. Stream 20 may include some amount of ethanol (and perhaps methanol, if ultra pure methanol was produced) and will be used as the basis of the aqueous makeup of the commercial formalin, Stream 21. In this manner, some of the ethanol may be recovered before the remainder is discarded in the liquid waste stream.

The formalin blender 136 combines stream 17 with a side stream of the waste water, stream 21, to produce formalin (37% formaldehyde, 6% alcohol by weight). This takes place at reduced pressures such that carbon dioxide will not readily absorb into the water-alcohol mixture. Formaldehyde, on the other hand, is completely miscible with the mixture. Similar to the scrubber, gases are passed over falling liquids, wherein formaldehyde enters into an aqueousstate, thus becoming formalin. The product stream continues on to storage and the carbon dioxide stream can be sequestered, processed, or incinerated and then vented.

While the disclosure has been illustrated and described as embodied in the method of and apparatus for producing methanol, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present disclosure.

Pawlak, Nathan A, Carr, Robert W

Patent Priority Assignee Title
10995685, May 16 2018 FUEL INJECTION TECHNOLOGIES CO , LTD Tri-fuel electric power generator
11505514, Apr 13 2016 LUMMUS TECHNOLOGY LLC Oxidative coupling of methane for olefin production
Patent Priority Assignee Title
1038547,
1500080,
1776771,
2007116,
2128909,
2196188,
2244241,
2384028,
2467993,
2722553,
2922809,
3027411,
3064029,
3130026,
3145220,
3232991,
3483229,
3689575,
3718006,
3920717,
3940428, Dec 30 1968 Imperial Chemical Industries Limited Methanol production
3975172, Mar 14 1973 Linde Aktiengesellschaft Recovery of gaseous components from scrubbing liquid
3977203, Mar 25 1974 University of Kansas Purification of natural gas by liquid/liquid extraction with a polar solvent
3993457, Jul 30 1973 Exxon Research and Engineering Company Concurrent production of methanol and synthetic natural gas
4067972, Jan 26 1972 Ciba-Geigy Corporation O-(Methyl or ethyl)-S-(propyl or butyl)-O-alkyl-(thio/sulfinyl/sulfonyl)-methylphenyl-thiophosphates
4144314, Oct 01 1976 Metallgesellschaft Aktiengesellschaft Process for regenerating water-containing methanol
4149940, Dec 22 1976 Imperial Chemical Industries Limited Methanol
4152407, Feb 02 1977 Process and apparatus for exothermic reactions
4203915, Jan 29 1976 Metallgesellschaft Process of producing methanol
4243457, Sep 02 1977 Sekisui Kagaku Kogyo Kabushiki Kaisha Method of molding pipe joints of reinforced resin
4243613, Sep 24 1977 Chemische Werke Huls Aktiengesellschaft Process for the manufacture of mixtures of formaldehyde and methanol by partial oxidation of methane
4252548, Jan 02 1979 Kryos Energy Inc. Carbon dioxide removal from methane-containing gases
4271086, Jan 29 1976 Metallgesellschaft Aktiengesellschaft Production of methanol
4289709, Dec 19 1979 Union Carbide Corporation Preparation of methanol from synthesis gas with promoted palladium catalysts
4289710, Dec 19 1979 Union Carbide Corporation Process for producing methanol from synthesis gas with palladium-calcium catalysts
4311671, Sep 14 1979 Imperial Chemical Industries Limited Synthesis reactor
4312955, Dec 01 1980 UNION CARBIDE CORPORATION, A CORP OF N Y Process for the production of methanol from synthesis gas
4324567, Dec 23 1978 Linde Aktiengesellschaft Separation of gaseous components from a gaseous mixture by physical scrubbing
4346179, Apr 05 1979 INSTITUT FRANCAIS Production of alcohols from synthesis gases
4353712, Dec 26 1979 Texaco Inc. Start-up method for partial oxidation process
4366260, Dec 17 1979 Unisearch Limited Catalysts for methanol synthesis
4374288, Dec 17 1980 Electromagnetic process and apparatus for making methanol
4386941, Dec 26 1979 Texaco Inc. Process for the partial oxidation of slurries of solid carbonaceous fuel
4392869, Dec 26 1979 Texaco Inc. High turndown partial oxidation process
4394137, Dec 26 1979 Texaco, Inc. Partial oxidation process
4400180, Dec 26 1979 Texaco, Inc. Partial oxidation process
4430316, Dec 18 1980 Linde Aktiengesellschaft Scrubbing system yielding high concentration of hydrogen sulfide
4443560, Jul 28 1982 M W KELLOGG COMPANY, THE, A DE CORP FORMED IN 1987 Adiabatically reforming a reformed gas for producing methanol
4476250, Aug 14 1982 The British Petroleum Company P.L.C. Catalytic process for the production of methanol
4479810, Dec 26 1979 Texaco Inc. Partial oxidation system
4490156, Dec 26 1979 Texaco Inc. Partial oxidation system
4530826, Dec 03 1980 Asahi Kasei Kogyo Kabushiki Kaisha Method for recovering and utilizing waste heat
4540712, Mar 31 1980 Union Carbide Corporation Process for producing methanol from synthesis gas
4564643, Dec 29 1982 Research Association for Petroleum Alternatives Development Process for the production of mixed alcohols
4575387, Apr 29 1983 Institut Francais du Petrole Process for separating a multi-component gaseous mixture
4606741, Aug 26 1983 Compagnie Francaise des Petroles; Institut Francais du Petrole Process for purifying natural gas
4608447, Mar 01 1985 The Standard Oil Company Process for the production of alcohols
4609388, Dec 01 1976 ACRION TECHNOLOGIES, INC Gas separation process
4614749, Mar 12 1985 Brookhaven Science Associates Low temperature catalysts for methanol production
4618732, May 20 1985 HER MAJESTY IN RIGHT OF CANADA AS REPRESENTED BY THE MINISTER OF ENERGY, MINES AND RESOURCES Direct conversion of natural gas to methanol by controlled oxidation
4619946, Mar 12 1985 Low temperature catalysts for methanol production
4623668, May 25 1983 BASF AKTIENGESELLSCHAFT, 6700 LUDWIGSHAFEN, GERMANY; LINDE AKTIENGESELLSCHAFT, 6200 WIESBADEN, GERMANY Preparation of methanol
4628065, Jun 21 1984 Institut Francais du Petrole Process for methanol synthesis from carbon oxides and hydrogen in the presence of a soluble copper and zinc catalyst
4628066, Feb 12 1986 Air Products and Chemicals, Inc. Process for the production of methanol
4670473, Aug 09 1985 Amoco Corporation Syn gas conversion
4721458, Mar 30 1985 Robert Bosch GmbH Gas feeding device for feeding a combustible gas mixture consisting of at least two components
4747858, Sep 18 1987 Air Products and Chemicals, Inc. Process for removal of carbon dioxide from mixtures containing carbon dioxide and methane
4760210, Jan 27 1981 Partial oxidation system
4782096, Sep 16 1987 Foster Wheeler USA Corporation Process for the production of synthesis gas
4816121, Oct 03 1983 QUEST AIR CASES INC Gas phase chemical reactor
4822393, Jun 30 1988 Kryos Energy Inc. Natural gas pretreatment prior to liquefaction
4861360, Feb 24 1984 Flexivol, Inc. Carbon dioxide absorption methanol process
4868221, Apr 03 1987 SHELL OIL COMPANY, A CORP OF DE Process for the production of methanol and a composition suitable for use as a catalyst in said process
4873267, Apr 29 1987 Shell Oil Company Process for the production of methanol and a composition suitable for use as a catalyst in said process
4888361, Sep 04 1987 Shell Oil Company Process for the production of methanol and catalyst composition for said process
4982023, Oct 16 1989 Mobil Oil Corporation Oxidation of methane to methanol
5012029, Oct 16 1989 Mobil Oil Corp. Conversion of methane
5015798, Dec 21 1989 Mobil Oil Corporation Conversion of methane
5063250, Jan 12 1988 Mitsubishi Gas Chemical Company Inc.; Mitsubishi Jukogyo Kabushiki Kaisha Process for the production of methanol
5067972, Jan 26 1989 AECI Limited Purification of gases
5132472, Oct 17 1990 Sun Refining and Marketing Company Catalytic oxidation of alkanes
5177279, Oct 23 1990 Mobil Oil Corporation Integrated process for converting methanol to gasoline and distillates
5180570, Jan 23 1992 M W KELLOGG COMPANY, THE A CORP OF DELAWARE Integrated process for making methanol and ammonia
5220080, Jun 29 1992 SUN COMPANY, INC Chromia on metal oxide catalysts for the oxidation of methane to methanol
5384335, Mar 26 1991 University of Pittsburgh Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite
5496859, Jan 28 1995 Texaco Inc Gasification process combined with steam methane reforming to produce syngas suitable for methanol production
5631302, May 10 1994 Metalgesellschaft Aktiengesellschaft Process of producing methanol
5735936, Apr 19 1995 Institut Francais de Petrole Process and apparatus for eliminating at least one acid gas by means of a solvent for the purification of natural gas
5770630, Sep 23 1986 Foster Wheeler Energy Limited Manufacture of organic liquids
5861441, Feb 13 1996 REG Synthetic Fuels, LLC Combusting a hydrocarbon gas to produce a reformed gas
5883138, Apr 25 1997 Exxon Research and Engineering Company Rapid injection catalytic partial oxidation process and apparatus for producing synthesis gas (law 562)
5886056, Apr 25 1997 EXXON RESEARCH & ENGINEERING CO Rapid injection process and apparatus for producing synthesis gas (law 560)
5959168, Oct 02 1996 Dow Global Technologies LLC Zeolite-based ethylabenzene process adaptable to an aluminum chloride-based ethylbenzene plant
6028119, Feb 27 1997 Mitsui Chemicals, Inc; Petroleum Energy Center Process for methanol production
6102987, Dec 05 1997 Krupp Uhde GmbH Process for the removal of CO2 and sulfur compounds from industrial gases, in particular from natural gas and raw synthesis gas
6139605, Feb 11 1997 Johnson Matthey PLC Gas absorption
6153149, Aug 06 1997 The Trustees of Princeton University Adaptive feedback control flow reactor
6159432, Jan 23 1997 The Board of Regents of the University of Oklahoma Conversion method for gas streams containing hydrocarbons
6267912, Apr 25 1997 EXXON RESEARCH & ENGINEERING CO Distributed injection catalytic partial oxidation process and apparatus for producing synthesis gas
6300380, Oct 02 1998 MITSUBISHI HEAVY INDUSTRIES ENGINEERING, LTD Production process for methanol
6328854, Apr 10 1998 REACTION 35, LLC Method of and apparatus for manufacturing methanol
6342091, Jan 22 1999 Krupp Uhde GmbH Method of removing carbon dioxide, sulphur compounds, water and aromatic and higher aliphatic hydrocarbons from industrial gases
6447475, Oct 10 1995 Pen Jet Corporation Gas power sources for a needle-less injector and needle-less injectors incorporating the same
6595291, May 29 1998 Naturkraft AS Process of preparing a gas composition and use thereof
6625988, Dec 11 2000 GENERAL ELECTRIC TECHNOLOGY GMBH Premix burner arrangement with catalytic combustion and method for its operation
6632971, Aug 30 2001 ExxonMobil Chemical Patents INC Process for converting natural gas to higher value products using a methanol refinery remote from the natural gas source
6645272, Sep 26 2000 Institute Francais du Petrole Process for deacidizing a gas by absorption in a solvent with temperature control
6667347, Sep 14 2001 CHEVRON U S A INC Scrubbing CO2 from methane-containing gases using an aqueous stream
6720359, Sep 14 2001 CHEVRON U S A INC Scrubbing CO2 from a CO2-containing gas with an aqueous stream
6726850, Jan 14 2000 EXXONMOBIL RESEARCH & ENGINEERING CO Catalytic partial oxidation using staged oxygen addition
6736955, Oct 01 2001 Technology Convergence Inc. Methanol production process
6881389, Sep 24 2002 EDG, Inc.; EDG, INC Removal of H2S and CO2 from a hydrocarbon fluid stream
6881758, Mar 05 2003 L'Air Liquide - Societe Anonyme a Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procedes Georges Claude Process and apparatus for the production of methanol
6942719, Jun 30 2003 Gas Technology Institute Methods and systems for pressure swing regeneration for hydrogen generation
7028478, Dec 16 2003 ADVANCED COMBUSTION ENERGY SYSTEMS, INC Method and apparatus for the production of energy
7067558, Mar 27 2002 Lurgi AG Process for the production of carbon monoxide and methanol
7071238, May 25 2001 BP Exploration Operating Company Limited; Davy Process Technology Limited Fischer-tropsch process in the presence of a coolant introduced into the reactor system
7083662, Dec 18 2003 Air Products and Chemicals, Inc Generation of elevated pressure gas mixtures by absorption and stripping
7108838, Oct 30 2003 PHILLIPS 66 COMPANY Feed mixer for a partial oxidation reactor
20010006615,
20020177741,
20030032844,
20030065042,
20040065199,
20040123523,
20040171701,
20060035986,
20060235088,
20060264683,
EP790226,
JP2004315413,
JP63001438,
RU2203261,
WO3031380,
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